JPS59188855A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve a shelf life at a high temp. after recording by providing a recording layer consisting of a resin having a specific structure and a quencher on a substrate. CONSTITUTION:A recording layer consisting of a resin which has an acid anion group at the side chain and is bound with cyanine cation in said acid anion group and a quencher is provided on a base body. The acid anion group is particularly preferably an anion group, etc. of a carboxylic acid, sulfonic acid, or phosphoric acid. The cyanine cation expressed by the formula I PHI<+>-L=PSI is preferable. PSI and PHI denote an indole ring, pyridine ring, etc. which may be condensated with an arom. ring. PHI and PSI are usually the same. L denotes a connecting group for forming a mono-, di-, tri- or tetracarbocyanine dye. The cyanine cation is incorporated at about 10-96wt% in the resin. The quencher is preferably a singlet oxygen quencher and is incorporated at generally about 0.05-12mol in 1mol the cyanine cation in the resin. The thickness of the recording layer is made usually about 0.03-10mum.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an optical recording medium, particularly a heat mode optical recording medium.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. Some devices perform writing by forming small holes, record information using the pits, and read out the bits by detecting them with read light.

As an example of such pit-forming media,
A recording layer consisting of a light-absorbing dye is formed on the substrate, and the dye is melted to form a bit, or a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye is formed. However, there are known ones that form bits by decomposing nitrocellulose, etc., and ones that form bits by coating a recording layer made of thermoplastic resin and light-absorbing dye and melting the resin and dye. .

The fifth dye, cyanine dye, exhibits an extremely high reflectance and can provide an extremely high readout S/N ratio.

However, in media that use such cyanine dyes, storage may cause the dyes to micromagne and get mixed into the substrate, reagglomerate, recrystallize, or bleed out, resulting in a decrease in writing sensitivity. , there is a disadvantage that the S/N ratio of reading may be lowered.

In particular, the readout S/N ratio decreases significantly due to high temperature storage after recording.

■ Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium using a cyanine dye that has improved storage stability, especially storage stability at high temperatures after recording. Our goal is to provide the following.

Such objects are achieved by the invention described below.

That is, the first invention is an optical recording medium characterized in that a recording layer made of a resin having seven acid anion groups in its side chain and a cyanine cation bonded to the acid anion groups is formed on a substrate. It is.

Further, the second invention provides a recording layer comprising a resin having an acid anion group in its side chain and cyani/cation/ bonded to the acid anion group, and a phenochar on the substrate. This is an optical recording medium characterized by the following.

(2) Specific Structure of the Invention The recording layer according to the present invention, which will be described in detail below regarding the specific structure of the present invention, is made of a resin having cyanine cations bonded to the side chains.

In this case, the resin to which the cyanine dye is bonded in the form of a cation is one in which one or more cations of the cyanine dye described below are bonded to the acid anion group of the resin side chain.

In this case, various acid anion groups can be used as the acid anion group in the side chain of the resin, but in particular, a carboxylic acid anion group (-CO
O-), sulfonic acid anion group (-SO3-), phosphate anion group, etc. are preferred, among which -COO-1-80
3'- is most preferred.

It is preferable to obtain such a resin having an acid anion group by alkali treatment of a -COOH-containing resin or a -8O3H-containing resin as described below.

1) C0OH-containing resin A homopolymer of acrylic acid or methacrylic acid or a copolymer with other monomers, or a copolymer of maleic anhydride, pyromellitic anhydride, trimellitic anhydride with vinyl acetate, etc. Polymers etc.

2) SO, H-containing resin polystyrene sulfonic acid etc.

The number of acid anion groups in the resin is about 0.05 to 2 per repeating unit.

In addition, there are no particular restrictions on the molecular weight, etc.
The dye is a cation of cyanine dye.

Among the cyanine cations, those represented by the following formula are preferred.

Formula CI) Φ” -L = F In the above formula [I], 1 and Φ may be fused with an aromatic ring, such as a benzene ring, a naphthalene ring, a phenanthrene ring, or an indole ring or a thiazole ring. , oxazole ring, selenazole ring, imidazole ring, pyridine ring, etc.

These Φ and 1 may be the same or different, but
They are usually the same, and various substituents may be bonded to these rings. Note that in Φ, the nitrogen atom in the ring has ten charges, and in V, the nitrogen atom in the ring is neutral.

As the skeletal rings of these Φ and W, the following formula [Φ]
It is preferable that it is represented by ~[ΦXV).

In addition, in the following, the structure is shown in the form of Φ.

()L,).

1 [Φ■] (R4)Q [ΦX] 几, [ΦX[I] (ox[:) (a,)t [ΦXV) R□' 1 Goose RYo Nitrogen in the 5 rings in various eggs such as this The group R bonded to the atom (two nitrogen atoms in the imidazole ring) (R□,
R1') is a substituted or unsubstituted alkyl group or aryl group.

There is no particular restriction on the number of carbon atoms in the groups R□, R□' bonded to the nitrogen atom in the ring.

In addition, if this group further has a substituent,
Substituents include sulfone group, hydroxyl group, carboxy group,
It may be an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxyoxy group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a halogen JjX group, or the like.

Further, when rings Φ and 1 are fused or non-fused indole rings (formulas [ΦI] to [ΦIN), two substituents R2゜R3 are preferably bonded to the 3-positions thereof. In this case, two substituents attached to the 3-position) 12.
R3 is preferably an alkyl group or an aryl group. Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

On the other hand, at a predetermined position in the ring represented by Φ and 1,
Furthermore, another substituent R4 may be bonded. Such substituents include various substituents such as an alkyl group, an aryl group, a heterocyclic residue, an alkyl group, an alkoxy group, an alkylthio group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a carboxy group. good.
And the number of these substituents (p, q, r, s,
t) is usually 0 or about 1 to 4. Note that when p, q, r, s, and t are 2 or more, the plurality of R4s may be different from each other.

Among these, those having a fused or non-fused indole ring of the formulas [ΦI] to [Φ■] are preferred.

This is because these materials have excellent coating properties and stability, exhibit extremely high reflectance, and have an extremely high readout S/N ratio.

On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye, especially when the formula [L
It is preferable that it is any one of I] to [L■].

Formula [LI] CH=: CH-CH= CH-C= CH-CH=
CH-CH formula CL II) CH=CH-CH=C=
CH=CH-CH formula [L■] CH-C=CH-CH Here, Y represents a hydrogen atom or a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, dimethylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxycarbonylpiperazine groups. Preferred examples include a di-substituted amine group such as Nato, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a nitro group, and a halogen atom such as Br and C1.

In addition, among these formulas [, I) to [Ll], tricarbocyanine linking groups, especially formulas (Lu) and (Lm) are preferred.

The cyanine dye O/ may be obtained by cationizing a cyanine dye that has been salt-formed with I, Br, CtO, BF4-2 according to a conventional method.

Next, specific examples of cyanino cations used in the present invention will be given, but the present invention is not limited to these.

Pigment rot Φ, 1! R, Ro-R2, R3D1
[Φwork] CH3CH3 D2 CΦ■) C, lH5C
ID3 [ΦI:] (CH2
)30HCH.

D4 (ΦI[) CH3C1
)I...D5 [Φm] (CH
,) 30HCH3D6 C0m, :]
(CH2) 30HCID7 (
Φkawa), C2H,, CH3D8
[Φm:] (CH2) 30COCI
-13CID9CΦnt)'
CH3CH3323- 1(, L Y - [t, B H - [L II ] H [Ll] H - [LI [,: l H - [Ln] H (Lm) H Dlo [Φ■] C□7H3, CH3D11
[ΦI]C4H0CH31)12 [tZI
I', ] C8H,,0COCH6CH.

1) 13 [Φr]C7H,,CH20H
CH.

D14 [ΦI[] C8H,,CH□
Dis (<2)III) C, H,,
OHCH,.

D]6 [Φm]〃CH1゜D17[ΦJ"]c7H14cα)C2H5C Horse D]8
CΦIII) C3H1, C14゜D
19 [Φ1 "] C. H37CH3D20
[Φ1) C8H, 7CHD21
[ΦI] C1,, H3, C00CH3CH
8゜-[LU, :l H-CLI[
] H-[Ln) H-CLIP) H-[L■]
H-[L■) H-[LI[:] H-CL II
) l-1-[LII]
HD22 [ΦI] C8H Yu.

0COCH3CH3D23 [Φwork] C8H□7
C2H5D24 [Φ■)'C, H 5
“2H5D25 CΦ■〕C□,
H4I, C00CH, CHD 26 [ΦII
] C,816CH,0COCI(3CH3
D27 [Φ■] Cl7H3, CH31) 2
s CΦ■〕C7H14Cα) CH3C2H
5D29 [ΦlI[] C7H0,C
H,OHCH3D30 [Φm] C7
H, CH20C”0C2H5CH3D 31
, [(1) m] C17H34COo
"2H5"H3D32 [Φm:)
"17H55"H3D33 [Φl[)
C, H□5 C2H5-' [Ln]
H”-[LI[] H-[Ln]
H-[Lm] H-[Ln] H-[L]II] H-[:Ltv
) H-(Lm)
H D34 [Φ■] C7H work, C
H3D35 [ΦtV] C□ヮH3,
-D3G [Φ■] C□,,H34CH
20COCH3-D37 [Φv]
C,, H5-D38 [ΦV]
CH-D39 [0w) C2H5-
D40 [Φv] C2H5-D41
[Φv:] C3H3-D42
[Φ■] C2H3- D43 [Φ■] C2H3- D44 [Φv:] C2H3--[
Lu] H CH3[LII,] HCH3[L
II) H4-CH [LIT]
H4-CHC
t, tB H-[LI[]
H5-C1(Lm) N(C6H5)25-O
CH3(1, II) H-[L■]
-1, [LI+] HD4
5 [Φv) C2H5-1)46
[0w)C
, H5=D47 [Φ■]C2H3- D48 [Φvr) C2H5-1)
49 [ΦW:] C2H5-1)
5 Q (Φ■) (CI-1,),
30COCH3-1)51 [ΦVl 3
CH2CH20H-1) 52 [Φ
輔] C2H,, -D53 [Φ■]C
3l (5- D54 [ΦK] C2H, - D55 [Φx] C,,H, - 056 [ΦX''] C2Hゎ
--[LI] H -CL I['3 CH3 -[Lvl H -' [Lvl H -[Lvn3 - - CLn+)]' N (C6H5)
25-C1[LII] H-[:LI]
H-[L11]14-[LII+)' 0CH3-[I,
I] H D57 [0M] CH2CH20H
-D58 [Φ■:] C2H3-
D59 [Φ■] (CH2) 30COCH3-D
60 [Φ beans)' C2H5-1
)61 [Φ store, l CH2CH2C
H20H-D62 [Φ■] C2
H5=D63 [ΦXIV] C2
H5-D64 [Φxv:] C2
H3-D65 [ΦVI:] C
8H17'D66 [Φ■]C□81437
-D67 [Φ■] C8H engineering,
-D68 [ΦVl]
C8H17--[Lll] H-[Lul H-[L II'] N C00C2H5
-[LulH-(LulN(C6H5),.

-CI, m) N(C6H5)2-
[L■] H-[Lm]
H4-CH3[Ln) H-[Lul
H - [Lm,] H s-Ct [Li3 H D69 [Φ■] C08H37-D70
[0M), C8H□7 (D7
1 [Φw'll' C8H engineering,
-D72 [Φ■] C8H work, -D
73 [Φ■] c18 horse 7 -D7
4 [Φ■] C8H work, -D75
[Φ■] C8H, -D76 [
Φ■] C engineering, H37-D77 [Φ■] C engineering. H
37-D78 [Φ■] C8H engineering, -
D79 [Φ■]08F1□7 - -D
80 [ΦNY) C3H17-=3: 5-Ct [Lm] H- - 5-□CH,, [L■) -5-CL
(t, nB −N(C6H5)
25-Ct [1, uD -N(C
61-1゜)2- [LB
H5-Ct [LT[]
H5-Ct [LulH - [Lv:] H - [L■] H - [L■]] - 6- D81 [Φ■] C8H, 7- D82 [Φ■] Cl8H37-1) 83
CΦ■〕C13H27-1)84 CΦ■
]C1,314□W-D85 [Φ■)
C3H07-D86 [Φ■1] C8
H□W -D87 [Φ■D C
l8H37-1) 88 [Φ■:]
C81-1□7-D89 [Φ■]
C work, H37=D90 [ΦX']C3
H1,7-D91 [ΦX,]C814,,ヮ
-D92 [Φ cut] C81-1□7
-- [L m ) N(C6H5
) 2[Lll) H -[JI[l] H -[LT[]H [1,tu]OCH3 -[L][]H (t, B H (Lm) N(CaH2) 2[L II ]
I-1 [Ln] H D93 [ΦX1l) C,,H,7-D
94 [Φ■] C8'l?
-D95 [ΦX11] C work. H37-D96
[Φ薙） C8H engineering, -D
97 [Φxl C8H engineering,
-D98 [ΦV'll C8H17-
1) 99'CΦ■]CH- 17 Dloo [Φtwin:l C5H1,7'DI
OI [0M) ”Hs
-5-Ct CL■) H-(
1t, m:) N(C,H5)2CL ll
i]N(C,H5) 2-[L■] H[Ln]
H[Lr+:]H[Lm)H[Lll]H-[LM)H Such a cyanine cation can be easily synthesized according to a known method.

That is, first, the corresponding Φ' -CH, , (Φ' represents a ring corresponding to the above Φ) is converted into an excess, for example, R11.
(ft is an alkyl group or an aryl group) to introduce R□ into the nitrogen atom in Φ' and Φ-CH5I
− is obtained. Next, this may be subjected to dehydration condensation using an unsaturated dialdehyde and an alkali catalyst. When this is reacted with a resin having an acid anion group, it bonds in the form of a cyanine cation.

Such a cyanine cation is bonded to the acid anion group through the N+ atom contained in the above.

To carry out such a bonding reaction, each of the above resins is treated in an alkali such as KOH-ethanol to obtain a resin having acid anion groups. Then, this and the cyanine dye are heated under reflux in a suitable solvent such as THF, cyclohegizano/dichloroethane, MEK, etc.
It may be extracted with water or the like.

The resin contains 10 to 95 wt of cyanine cations.
%, especially about 50 to 6 wt%.

The recording layer of the medium of the present invention is made of a resin to which such cyanine cations are bonded, and the recording layer contains:
Separately, other oils may be included. In this case, the coating properties are improved, and the recording sensitivity, readout S/N ratio, etc. are improved.

As such resin, for example, Japanese Patent Application No. 58-1.5
Those described in No. 229 and the like are suitable.

The resin is contained in an amount of about 50% or less by weight based on the resin to which cyanine cations are bonded.

Preferably, such a recording layer further contains a quencher.

This reduces reproduction deterioration and improves light resistance.

As a quencher, you can use anything divine, but especially when the cyanine cation is excited and singlet oxygen is generated, it undergoes electron transfer or energy transfer from the doublet oxygen and becomes an excited state, and then returns to the ground state by itself. It is preferable to use a singlet oxygen salt which converts doublet oxygen into a triplet state at the same time.

Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with cyanine cation-binding resins. It is preferable. In this case, the central metal is a tooth, C01Cu
, Mn, etc. are preferred, and the following compounds are particularly preferred.

1) Acetylacetonate chelate QI Ni (1) Acetylacetonate QzCu (]
I) Acetylacetonate Q3Mn(ft[)Acetylacetonate Q4CO(l[)Acetylacetonate 2
) Bisditheo-α-diketone system Here, 茫) to d41 represent a substituted or unsubstituted alkyl group or an aryol group, and M represents a divalent transition Kinjo atom.

In this case, M has a single charge and may form a salt with a quaternary ammonium ion or the like.

Q5Ni (1) dithiobenzyl Q5 Ni (If) dithiobiacetyl Q9 N''-(C4H9)! 3) Bisphenyldithiol system Here, 5' and halo) are alkyl groups such as methyl group, or Ct etc. Represents halo, gun atom, etc., M
represents a divalent transition metal atom such as Ni. Furthermore, a
and b are each 0 or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with an anion/anion, and further, other ligands may be bonded above and below M.

As such, the following is QIOPA-1
001 (Product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (Same as above Ni-bis(toluenedithiol)tetra(1-butyl)ammonium) Qx2PA-1oo3 (Same as above) Q13 PA-1005 [Same as above Ni-bis (dichlorobenzenedithiol)tetra(1-butyl)ammonium] Q14 PA-1006 (I ditto N1-bis(trichlorobenzenedithiol)tetra(1-butyl)ammonium) Q15CO-bis(benze/-1,2-dithi, t-le)
Tetra-butyl ammonium Q16Co-bis(0-xylene-4,5-dithiol)tetra(1-butyl)ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis(0-xylene-4,5-dithiol) -dithiol)tetrabutylammonium Q19Ni-bis(5-chlorobenzene-1゜2-dithiol)tetrabutylammonium Q20Ni-bis(3,4,5,6-titramethylbenzene-1,2dithiol)tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol)tetrabutylammonium 4)dithiocarbamate chelate system where R72 and R(8) represent an alkyl group.

Furthermore, M represents a divalent transition metal atom.

Q22 Ni-bis(dibutyl dithiocarbamic acid) [A/Tigey NBC (manufactured by Sumitomo Chemical Co., Ltd.]) 5) Bisphenylthiol type Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate type Here, M is divalent represents a transition metal atom. Also, M
has a single charge and may form a salt with an anion,
Benose/ring (may have a substituent group)

Q24 Ni-bis(thiocatechol)tetrabutylammonium 7) Salicylaldehyde oxime system return 11 Here, R9) and RQI represent an alkyl group,
M represents a divalent transition metal atom.

Q25 Ni (11) O-(N-inglobylformimidoyl)phenol Q26 Ni (II) O-(N-dodecylformimidoyl)phenol Q27 Co(TI)O(N-dodecylformimidoyl)phenol Q28 Cu (It) 0-(N-dob'/ )b
(formimidoyl) phenol Q29 Ni (II) 2.2'-(trilomethylidine on etele7bis)]-diphenol Q30 Co (11) 2.2'-(trilomethylidine on ethylene bis)]-diphenol Q31 Ni (II ) 2.2'-C1゜8-naphthylene bis trilomethylidine), :) -Diphenol Q32 N1(I[) (N-phenylformimidoyl) Phenol Q33 Co(I[) (N-phenylformimidoyl) Q34 Cu (1)- (N-7x=l*lumimidoyl)phenol Q35 Ni (n) salicylaldehyde phenylhydrazone Q36Ni (u) salicylaldehyde oxime 8) theobisferrotochelate system, where M is the same as above; , 傅υ and 傅2 represent an alkyl group. Further, M has one charge and may form a salt with an anion.

Q37 Ni (I[) n-phthylamine/[:
2,2'-thiobis(4-tert-octyl)
- 7 x 7 v-t) [Cyasorb -
UV-1084 (American Cyanamid Co., Ltd.) Q38Co(I[)n-butylamide/[2,2'-thiobis(4-tert-octyl)-ferulate] Q39 Ni(II)-2.2'thiobis( 4-t
ert-octyl)-ferulate 9) Phosphonous acid chelate-1-type α-d Here, M is the same as above, and cylindrical and p represent a substituent such as an alkyl group or a hydroxyl group.

40 In addition to this, other quenchers include the following.

10) Benzoate Q51 Existing chemical substance, 3-3040 (Tinupino-1
20 (manufactured by Chibakaiki)] 11) Hindered amine Q52 Existing chemical substance 5-373211: ULI to SA
, S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such an entcher is synthesized according to a known method.

The quencher is generally 0.05 to 12 mol, particularly 0.05 to 12 mol, particularly 0.
It is contained in an amount of about 1 to 1.2 moles.

In addition, the maximum absorption wavelength (λmax) Q of Que 7 Cha is:
Maximum absorption eJC (λmax) of cyanine cation used
It is preferable that it is D or more.

In this case, (λmax)Q(λmax)D is preferably O or 3500 m or less.

As a result, reproduction deterioration becomes extremely small.

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method.

The thickness of the recording layer is usually about 0.03 to 10 μm.

In addition, such a recording layer may contain other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, crosslinking agents, etc. It's okay.

To form such a recording layer, it may be applied onto the substrate using a predetermined solvent and dried.

Examples of solvents used for coating include keto/types such as methyl ethyl keto/, methyl imbutyl ketone, cyclohexa, and horn, ester types such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, and methyl cellosolve. , ether type such as ethyl selonulf, aromatic type such as toluene/hydrogen, halog/argyl type such as dichloroethane, alcohol type, etc. may be used.

The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc.

Further, its shape may be any shape such as a chi-two, a disc, a drum, a belt, etc. depending on the intended use.

Note that the base body usually has a groove for tracking.
Further, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc.

Further, as the substrate material, a substrate without grooves or grooves such as acrylic resin, polycarbonate resin, highly heat-resistant epoxy resin, polycarbonate resin, polysulfon resin, polyether sulfon, methylpentene polymer, etc. is suitable.

These substrates can also be coated with nib primer on the substrate to improve solvent resistance, wettability, surface tension, thermal conductivity, and the like.

As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, etc. can be used.

In addition, on the recording layer, if necessary, a reflective layer that functions as a back surface when using a transparent substrate, various uppermost protective layers, etc.
It is also possible to provide a single layer or the like.

The medium of the present invention may have the recording layer described above on one surface of such a substrate, or may have recording layers on both surfaces thereof. In addition, two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, and the substrate is sealed to prevent dust and scratches. You can also choose not to have one.

(2) Specific Effects of the Invention The medium of the present invention is irradiated with recording light in pulses while running or rotating. At this time, the resin itself melts due to the heat generated by the cyanine oxide in the recording layer, forming a bit.

The bits formed in this manner are read out by detecting reflected or transmitted light, particularly reflected light, from the read source while the medium is running or rotating.

In this case, recording and reading may be performed from the base side or from the recording layer side.

It is also possible to erase the bits once formed in the recording layer with light or heat and rewrite them.

In addition, as the recording or reading light, semiconductor laser, He-Nev-zar, Arv-zer, He
-Cd laser etc. can be used.

V. Specific Effects of the Invention According to the present invention, even if a medium is stored for a long period of time, there is very little deterioration in writing sensitivity or S/N ratio. In particular, the deterioration of the S/N ratio when read after recording and storage at a high temperature is extremely small.

Furthermore, since cyanine dye is used, the readout S/N ratio is also extremely high.

In addition, according to the second invention, regeneration deterioration is significantly reduced,
Extremely high light resistance.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

EXAMPLES Resins A, B%C below were treated in KOH-EtOH to introduce acid anion groups.

This, iodide of cyanine dye D9 and D44
Eye of. After refluxing the dye in THF-methanol for 2 hours, it was poured into water, and Soxhlet extraction with water was performed to remove K I.

As a result of elemental analysis of the products thus obtained, no bald 1-j was detected, and it was confirmed that a cyanine cation was bonded to the acid anion group. Note that the amount of dye in the molecule was about 79 wt%.

Each of these cyanine cation-binding resins was dissolved in dichloroethano, and placed on a substrate made of polymethyl methacrylate.
A recording layer was formed with a rinsing thickness of 0.07 μm.

Separately, for comparison, a recording layer was formed in which the above cyanine dye and resin were blended at a weight ratio of 7:3.

Note that the resins R1, R2, and R3 are as follows.

ttl Polymethacrylic acid 112 Styrene/methacrylic acid (50150 mol)
Copolymer R3holJ-paratoluenesulfonic acid For each sample thus prepared, 1800
While rotating at rpm, a semiconductor laser (830 nm) is focused from the back side of the substrate to a diameter of 1μ.
Writing was performed with a pulse r1 of 100 nsec.

After this, the l mW semiconductor laser readout light was applied for 1 μs.
A pulse with a width of 3KH2 was irradiated from the back side of the substrate, and the reflected light was detected to measure the C/N ratio.

Each sample was then incubated for 10 minutes at 50°C and 90% relative humidity.
After storage for 00 hours, the deterioration of the C/N ratio was measured.

Table 1 shows the deterioration rate (%) of the C/N ratio after storage.

From the results shown in Table 1, the effects of the present invention are clear.

Examples In sample 7F61 of Experimental Example 1, 50% by weight of quencher-Q14 was added to the cyanine cation binding resin.
Sample A15 was obtained.

Table 2 shows the reproduction deterioration rate (%) of the C/N ratio after samples /161 and 415 were continuously irradiated with readout light for 4 minutes.

Table 2 High temperature storage deterioration 11 Reproduction deterioration 352 From the results shown in Table 2, the effect of the second invention is clear.

Applicant: TDC Co., Ltd. Agent, Patent Attorney: Yo Ishii - Teito Kanyu Seishi (self-motivated) June 2, 1981 Patent Crime No. 63947 2, Title of Invention: Optical Recording Media 3 , Relationship to the case of the person making the amendment Address of the patent applicant
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building, 1st Floor Telephone: 988-16806 The statement in column ``3. Detailed Description of the Invention j'' of the Statement of Contents of Amendment is amended as follows.

Mnj means fNi, Co, Cu, Mn.

Pd and Ptj are corrected.

“1) Acetylacetonate chelate QINi (I
I) Acetylacetonate Q2 Cu(II) Acetylacetonate q3 Mn(m) Acetylacetonate Q4 Co(II) Acetylacetonate 2) Hisdithio-α-diketone system Here, R(1)-R(4) is, Represents a substituted or unsubstituted alkyl group or aryl group, M is Ni, C
represents a transition metal atom such as o, Cu, 'Pd, Pt, etc.

In this case, M has a single charge and may form a salt with a cation such as a quaternary ammonium ion.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl Q7 "(04H8)4 3) Hisphenyldithiol system (5) (6) Here, R and R are an alkyl group such as a methyl group, or an alkyl group such as C1 /\ represents a loken atom, etc., and M is Ni, Co.

Represents a transition metal atom such as Cu, Pd, PL, etc. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, other ligands may be bonded above and below M.

Examples of this include the following:

QIOPA-1ool (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (same as Ni-his(toluenedithiol)tetra(butyl)ammonium) Q12 PA-1'o03 (same as above) Q13 FA
-1005 (same as above Ni-bis(dichlorobenzene)
Tetra(t-butyl)ammonium] Q14 PA-1006 (same as above Ni-bis(trichlorobenzenedithiol) tetra(t-butyl)ammonium) Q15 Co-bis(benzea-1,2-dithiol)tetrabutylammonium Q16 Co- Bis(0-xyL/n-4.5-dithiol)teto1(t-butyl) Ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis(o-xyL/7-4. 5-dithiol)tetrabutylammonium Q19 Ni-bis(5-chlorohensen-1.2
-dithiol) Tetrabutylammonium Q2ONi-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)Tetrabutylammonium Q21Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) Tetrabutylammonium 4) Dithiocarbamic acid chelate system (?) (8) Here, R and R represent an alkyl group. Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd or PL.

Q22Ni-bis(dibutyl dithiocarbamine M) [
Anchiken NBC (manufactured by Sumitomo Chemical Co., Ltd.) 5) Bisphenylthiol-based Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate-based where M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as pt. Further, M has a single charge and may form a salt with a cation, and the benzene ring may have a substituent.

Q24Ni-bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime system (9) Here, R and R (10) represent an alkyl group,
M is Ni, Co, Cu.

Represents a transition metal atom such as Pd or Pt.

Q25 Ni (II) o -(N-isopropylformimidoyl) phenol Q26 Ni (II) o - (N-dodecylporumimidoyl) phenol Q27, Co (II) o - (N-dodecylporumimidoyl) Phenol Q28 Cu (II) o -(N-dodecylpormimidoyl) Phenol Q29 Ni (n) 2.2'-(trilomethylysine on ethylene hiss)]-diphenol Q30 Co(11) 2.2'-( ethylene bis trilomethylidine)] -diphenol Q31 N1(IT)2.2'-(1,8-naphthylene bis trilomethylidine)] -diphenol Q32 Ni (II)-(N-7enylformimitoyl)phenol Q33 Co (II)-(N-phenylpolumimidoyl)phenol Q34 Cu (II)-(N-7,-=-lupormimitoyl)phenol Q35 N1(II) Salicylaldehyde Phenylhydrazone Q36 N1(II) Salicylarte (human oxime) Thiobisferrate chelate system R (11) R (12) (11) Here, M is the same as above, and R (12) and R represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 N1(II) n-butylamino[2゜2'-
Thiobis(4-tert-octyl)-ferulate)
(Cyasorb-UV-1084, (American Cyanamid Co., Ltd.)
) Q38 Co ('II) n-butylamino[2゜2'-thiobis(4-tert-octyl)-
Ferulate] Q39 Ni (II)-2,2'-thiohis(4
-tert-octyl)-ferulate 9) Phosphonous acid chelate system Here, M is the same as above, R(13) and (14) and R represents a substituent such as an alkyl group or a hydroxyl group.

40 There is something like that.

10) Henshade Q41 Existing chemical substance 3-3040 (Tinuvin-1
20 (manufactured by Chihekaigyi)] 11) Hindered amine Q42 Existing chemical substance 5-3732 (5ANOLL
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]

Claims (1)

[Claims] 1. An optical recording medium comprising a recording layer made of a resin having an acid anion group in its side chain and a cyanine cation bonded to the acid anion group on a substrate. . 2. An optical recording medium comprising a recording layer formed of a resin having an acid anion group in its side chain and a cyanine cation bonded to the acid anion group, and a phenochar on a substrate.